The geometry of six stereoisomers of pentacyclo[8.2.1.1(4,7).0(2,9).0(3,8)] tetradecane formed in [2+ 2] cycloaddition reaction of bicyclo[2.2.1] hept-2-ene (norbornene) were optimized by a theoretical method at the DFT level with the B3LYP functional. The calculated GIAO H-1 and C-13 shieldings were transformed to chemical shifts (delta) on the TMS scale and next compared with those obtained experimentally for two stereoisomers. The H-1 and C-13 NMR chemical shifts calculated using the DFT method were found to be in very good agreement with the available experimental data. This is the first example of studying the [2+ 2] cycloaddition products of norbornene by theoretical method. (C) 2011 Elsevier B. V. All rights reserved.